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THE CATALYTIC PREPARATION OF HYDROXYLAMINE 



BY 

VALENTINE AUSTIN JONES 
B. S. University of Illinois 
1921 

THESIS 

Submitted in Partial Fulfillment of the 
Requirements for the Degree of 
MASTER OF SCIENCE 
IN CHEMISTRY 

IN 

THE GRADUATE SCHOOL 

OF THE 

UNIVERSITY OF ILLINOIS 



1922 



UNIVERSITY OF ILLINOIS 



THE GRADUATE SCHOOL 



Ja nuary 19, 192J? 



I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 



SUPERVISION BY- 



Valenti n s Aust in jLcnes 



ENTITLED The Catalytic Preparation cf K ydroxylarjjn e 



BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
THE DEGREE OF jjas t ery_of Science 




Recommendation concurred in* 



Committee 

on 



Final Examination* 



*Required for doctor’s degree but not for master’s 



438978 



Digitized by the Internet Archive 
in 2016 



https://archive.org/details/catalyticpreparaOOjone 



Acknowledgment 

The writer wishes to express 
his appreciation and sincere 
thanks to Doctor J.H. Reedy 
for his assistance in the 
experimental work, and also 
for his aid in writing this 



thesis 



Table of Contents 



I. Introduction. 

II. Historical. 

III. Purpose of Research. 

IV. Experimental. 

V. Discussion. 

VI . Summary . 

VII. Bibliography. 



The Catalytic Preparation of Hydroxylamine . 



I . Introdu c tion . 

The question of procuring a good yield of Hydroxylamine 
by a simple and inexpensive method has been the subject of consi- 
derable investigation by chemists for many years. A few methods 
have been suggested and used for its preparation, but in all the 
yields are not good, and the methods of separation from by-products 
are difficult and not conducive to complete separation. Reduction 
of nitrites , nitric acid and nitric oxide to Hydroxylamine by such 
reducing agents as sulphurous acid, chromous chloride, hydrogen 
sulphide .hydrogen, etc. , have been attempted with but indifferent 
success , mainly , because of the fact that a good method of separation 
was lacking or that the reduction did not stop at Hydroxylamine, 
but continued further to give nitrous oxide, nitrogen or ammonia. 

It was noticed by Victor Meyer and others that often some 
substance used as a catalyser or by-products of the reactions 
would cause the immediate decomposotion of any Hydroxylamine which 
might be formed. The urgent need of a catalyser which could be used 
to facilitate the reduction of nitric oxide to Hydroxylamine alone 
and still not cause the decomposition of the Hydroxylamine formed, 
seeias a paramount necessity if we expect to obtain Hydroxylamine 
in nearly theoretical amounts. 























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II* Historical 



In 1834 Faraday ' published an article wherein he described 
some experiments on the use of platinum sponge as a catalyser. 

Among the reactions he experminted with was the reduction of nitric 
oxide by means of hydrogen using the platinum sponge as a catalyses 
He passed a mixture of hydrogen and nitric oxide slowly over pla- 
tinum sponge at room temperature. Reduction of the nitric oxide 
took place but his final product was not Hydroxylamine as he ex- 

X 3 

pected but ammonia and water. F.Kuhlmann and Jouve“also working 
on the reduction of nitric oxide by hydrogen with the use of pla- 
tinum sponge as a catalyser obtained ammonia and water as the 
final product, altho Jouve working at temperatures not exceeding 
115°C, claims to have obtained 1-2 % of Hydroxylamine. 

Cooke working with a mixture of nitric oxide and hydrogen 
and using platinum sponge as a catalyser , states that he obtained 
ammonia, Hydroxylamine and nitrous oxide, the amounts of which he 
does not mention in his paper. He states that if one uses nitric 
oxide and hydrogen in the volume ratio of 1-2, the following re- 
action will take place 

2N0 +- H2 H20 + N20 

and for 2 volumes of nitric oxide and 8 volumes of hydrogen the 
equation is 

2N0 + 4H2 —NH20H NH40H 

Sabatier and Senderens, - Neogie and Adhicary used nickel and 
copper as catalysers. They passed a mixture of nitric oxide and 



of 



hydrogen thru a glass tube which contained finely divided nickel 
or copper at temperatures ranging from 150-250 'C. The resulting 
product was ammonia and nitrogen. 

According to Divers and Hagaf Dummreicher* and Chesneau,^ 
Hydroxylamine and ammonia are produced when nitric oxide is passed 
thru a series of gas-washing bottles containing tin and cone, 
hydrochloric acid.. The yields, however, are small and the separa- 
tion of the Hydroxylamine hydrochloride is not easily accomplished. 

Chesneau 1 ' experimenting with a solution of chromous chloride 
claims to have reduced nitric oxide to Hydroxylamine and ammonia. 

He points out that a rapid constant amount of nitric oxide must 
be passed into an acid solution to form Hydroxylamine, otherwise 
a slow stream will cause the formation of ammonia. 

Ludwig and Hein, Divers and Haga" published papers in which 
they state that Hydroxylamine can be obtained in considerable 
amounts if nitric oxide is passed slowly into a heated mixture 
of tin and hydrochloric acid. They do not state the yields ob- 
tained by this method. 

Chromous chloride solution according to Chesneau and Kohl- 
schutter" reduces nitric oxide to ammonia in neutral solutions 
while in acid solution it reduced to Hydroxylamine . The same 
authors also found that hydroiodic acid reduces nitric oxide to 
ammonia and nitrous oxide. 

)3 

Dummreicher reports that stannous chloride in strongly acid 
solution will reduce nitric oxide to Hydroxylamine in small 
amounts and not readily. 



/*- 

Hans Ziehl attempted to prepare Hydroxylamine by the reduc- 





tion of nitric oxide using a colloidal solution of platinum, which 
he prepared by reducing a sightly alkaline solution of chlor- 
platinic acid with hydrazine and adding a small amount of gum 
arabic. Equal volumes of hydrogen and nitric oxide were passed 
under pressure into a pressure bottle containing the colloidal 
platinum. The bottle is connected to a shaking devise and sha- 
ken vigerously. Ziehl found that no Hydroxylamine was formed by 
this method but that his final product consisted of ammonia and 
nitrogen. A mixture consisting of 2 volumes of nitric oxide and 
3 volumes of hydrogen was tried but as before he obtained ammonia 
and nitrogen. They found that 82.34$ of the nitric oxide was 
changed to nitrogen while 15.73$ became ammonia. 

Divers and Haga'have succeeded in obtaining Hydroxylamine 
in the following manner. If sodium sulphide and sodium nitrite 
in solution are mixed, then acidified and boiled, Hydroxylamine is 
formed, and when the sulphide is in the proportion of 2 mols to 
1 mol of the nitrite, and the hydrochloric acid added very slowly, 
almost all of the nitrogen is found on titration with iodine to 
have been converted into Hydroxylamine. 

NaN02 -r 2Na2S03 + HOH t RHCL — ^NH20H,HC1 3Nacl 2NaHS04 

On evaporating the acid solution, separating the sodium salts by 
absolute alcohol and evaporating again, Hydroxylamine sulphate 
separates out. Further experiment proved that sodium meta- 
sulphide used with sodium nitrite gave the best yield of Hydroxy- 
lamine sulphate. 

In 1387 Raschig reported that Hydroxylamine can be gotten 



from a nitrite by sulphonation followed by hydrolysis. Divers 







.... it m 'M 111. I 

* 













3 

and Haga working on the suggestion given by Raschig's work used a 
concentrated solution of 2 raols of commercial sodium nitrite, 1 mol 
of sodium carbonate and then treated the solution with sulphur 
dioxide until just acid, while it was kept well agitated at2-3'"C 
below zero. It was claimed by them that at this temperature sul- 
phur dioxide will not act on Hydroxylamine but will reduce the 

nitrite completely. At this temperature the conversion of the ni- 

S * 2 

trite into oximido-sulphonate^'^v, c r<? A< * appears to be complete. 

~ O A'<X’ 

When gently warmed with a few drops of sulphuric acid, the oximido- 
sulphonate rapidly by hydrolysis, with mark rise in temperature into 
oxyamido-sulphonate and sodium acid sulphate. The solution of the 
salts is kept at 90-95 G for two days, by the end of which time all 
the oxyamido-sulphonate will have hydrolysed into Hydroxylamine 
sulphate. 

B. B.Adhikary in writing on the reduction of nitric oxide 
by contact action of metals and metallic oxides states that he 
passed a mixture of nitric oxide and hydrogen over gold, silver, 
magnesium, tin, antimony , bismuth and iron at various temperatures and 
in all cases ammonia and water were the final products. 

Z) 

E.P.Schoch and R.H. Pritchett after trying various other 
methods found that the preparation of Hydroxylamine by the electro- 
lytic reduction of nitric acid according to the method of Julius 
Tafel, to produce the largest yields. The apparatus used was iden- 
tical with that of Tafel f s except that the anode is a lead rod or 
pipe about one inch in diameter; this was used in place of the 
graphite anode employed by Tafel, because they found it necessary to 
use dilute sulphuric acid in the anode compartment. The Hydroxyla- 



mine hydrochloride was freed from the accompanying ammonium chloride 
produced, by extraction with cold absolute alcohol. They claim to 
have obtained about 80 % of the theoretical amount possible. 

Other work too numerous to mention has been done upon the 
preparation of Hydroxylamine , but the methods are only of theoretical 
importance and therefore will not be mentioned here. 

III. Purpose of Wo rk. 

As it will be seen from the preceding pages, very few exper- 
iments have been performed using a catalyist for promoting the re- 
duction of the nitric oxide to Hydroxylamine. In view of the diffi- 
cult methods used for recovering Hydroxylamine from the by-products 
by the reaction it was deemed that, if possible , some method might be 
devised for preparing Hydroxylamine by the use of two gases, one of 
them to be nitric oxide and the other some reducing gas as sulphur 
dioxide, hydrogen, hydrogen sulphide, etc . , in the presence of a cat- 
alyist. In this manner interfering by-products would be eliminated 
and the Hydroxylamine easily and quickly separated. It will be noti- 
ced from Ziehls and Sabatier and Senderens (loc. cit.) work using 
colloidal platinum and nickel respectivily , that the reduction does 
not stop at Hydroxylamine but continues to ammonia. To secure a 
catalyist which would promote the reduction of nitric oxide to 
Hydroxylamine and stop there, seemed to be the key to the solution of 
this problem, so it was thus made the object of this paper. It was 









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PH 

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thot advisable to undertake various methods of reduction and deter- 



mine the effect different catalyist had on the reaction. Once the 
reduction of nitric oxide to Hydroxylamine was accomplished, a 
method 02 separation and purification would be a comparatively sim- 
ple task because of the absence of interfering substances. 

Altho Schoch and Pritchett (loc.cit.) xhave obtained 
Hydroxylamine by the electrolytic reduction of nitric acid and 
claim to have obtained as much as 80 % of the theoretical yield, we 
did not attempt to obtain Hydroxylamine by an electrical method but 
have confined ourselves to its production by strictly chemical 
means. 

The method to be used for the detection Hydroxylamine was 
the reduction of Fehling's solution. Very minute amounts of 
Hydroxylamine of its salts are sufficient to cause the formation 
of the brown copper oxide. 

IV. Experimental . 

According to Sabatier and Sendereiis (loc.cit.) the activity 
of nickel as a catalyist is nil at low temperatures, but at 250-300' 0 
nickel is quite active. It was decided to see if nickel at a tem- 
perature of 100-115°C would catalyse the reduction of nitric oxide 
to Hydroxylamine, and not to ammonia. The apparatus used is shown 
on Figure 1 . 

Preparation of Catalys err-The catalyser was made by melting 

nickel nitrate in its own water of crystalization in a nickel cruci- 



ole and then inpregnat ing animal charcoal with the solution. The 
inpregnated charcoal was then heated in the crucible to form the 
nickel oxide. It was placed in a glass conbustion tube heated to 

c 

^50-300 C,and reduced with a stream of hydrogen for three hours. 

Procedure — 3he tube, after the reduction of the nickel 
oxide had taken place, was allowed to cool slowly to 105 G with 
hydrogen still passing thru. A mixture of 2 volumes of hydrogen 
and one volume of nitric oxide was slowly passed thru the tube, the 
temperature being maintained about 110 C,the alkaline gases pro- 
duced were absorbed in dilute hydrochloric acid. When the run was 
completed this acid solution was examined for Hydroxylamine by 
adding a little of the solution to Fehling's solutions. No reduc- 
tion of the Fehling's solution occured which proved the absence of 
Hydroxylamine. On opening the tube it was found to smell very 
strongly of ammonia. The hydrochloric acid solution was evaporated 
lo dryness on a water bath, the residue broken up and again tested 
for Hydroxylamine and ammonia. No Hydroxylamine hydrochloride was 
found to be present but on heating a little of the residue with so- 
dium hydroxide , the odor of ammonia was easily detected. Another 
run was made using equal volumes of nitric oxide and hydrogen but 
as before ammonia was the final product. 

A statement is found in many text books that Hydroxylamine 



can be prepared by passing nitric oxide thru a solution of tin- 
dissolving in hydrochloric acid. No mention,however , is made in 
regards to the amounts obtained and so in order to get some idea 




of the yield of Hydroxylamine produced, by this method, it was deci- 
ded to repeat the procedure using metallic mercury as a catalyser. 

Procedure - -The apparatus is shown in Figure 2. In each of 
the gas washing bottles was placed tinfoil cut into very small 
squares, and covered with a dilute solution of hydrochloric acid. 

The two gases nitric oxide and hydrogen in equal volumes were 
bubbled thru the bottles at a uniform rate of approximately 30 
bubbles per minute. The tin in dissolving gives up nascent hydro- 
gen according to the equation 

Sn 2H01 = SnC12 + H2 

which was expected to x-educe the nitric oxide while stannous chlor- 
ide ana mercury might catalyse the reduction. After fourteen liters 
of each gas had been passed thru the bottles, the solutions from 
each of the bottles were combined in a large Erlenmeyer flask, water 
added and the tin precipitated out with hydrogen sulphide. Two pre- 
cipitations were necessary to separate alx of uhe tin. T**e solution 
was then filtered, washed and the filtrate evaporated to dryness on 

a water bath, ihe residue was examined for Hydroxylamine but no 
reduction of Fehling’s solution occured. It was then tested for 

ammonia which was found to be present, mercury being omitted anot- 
her run similar to the first gave ammonia as the only product. 

It was apparent from the preceding experiments that if 
satisfactory yields are to be obtained a more intimate and longer 
contact should be made between the gases and the catalyser* With 
this idea in mind an apparatus as shown in Figure 3, was constructed. 



Apparatus - -This consisted of an tight cast iron cylinder 
about .3 feet tall and 8 M in diameter. The valve at the top was used 
to regulate the flow of the gases while the one at the bottom was 
connected with the water main by means of which, water could be for- 
ced in compressing the gases to o.ny required pressure up to 40#. 

By means of a hollow copper „ube bent in spiral shape the gases 
could be connected to a pressure bottlewhich was mounted on a 
shaking devise. Nitric oxide was prepared by mixing in a flask, 

200 grams of ferrous sulphate with 40 grams of potassium nitrate 
and dropping hot dilute sulphuric acid on the mixture, the gas evol- 
ved being collected in gasometers. The gas cylinder was filled 
with water, the hollow copper tube connected with the gasometer and 
the gas forced in under a water head contained in a connecting 
gasometer. The valve at the bottom of the cylinder being opened 

simultaneously with the valve at the top. After twelve liters of 
nitric oxide had been forced in both valves were closed and connec- 
tion made with a hydrogen tank. The upper valve was then opened 
and hydrogen forced in until the gauge on the cylinder showed 25# 
pressure, after which the valve was closed. In the pressure bottle 
was placed a colloidal solution of platinum prepared according to 

directions given by H.L.Lockte of the University of Illinois. 

Prepa r ation of Gatal.yist --About .3 gram of platinum was 
dissolved in aqua regia and evaporated to dryness twice, then taken 
up with hydrochloric acid. The chlor-platinic acid thus formed 
was poured into a beaker containing 250 c.c.of water made slightly 
alkaline with sodium hydroxide. 



Approximately .3 gram of gum arable in water solution was added, 
and a few crystals of hydrazine hydrochloride were dropped into the 
solution. Reduction took place almost immediately after which the 
solution was made acidic with hydrochloric acid. The solution was 
poured into the pressure bottle, the bottle evacuated and connection 
made to the gas cylinder. 

Procedure - -The motor was started and the solution 
shaken for six hours during which time the reading on the gauge 
was carefully noted. No decrease on the gauge reading was observed 
during the run. The bottle was then disconnected and the solution 
poured into a flask containing a volume of acetone equal to that 
of the solution. This acetone solution wa3 allowed to stand over 
night and then filtered to remove the precipitated platinum. The 
filtrate was then tested for Hydroxylamine with Fehling '3 solution, 
but no reduction was observed. On evaporating the solution to dry- 
ness no residue was left proving that nitric oxide and hydrogen in 
the presence of colloidal platinum would not react. 

Platinum as the Catalyist --A active form of platinum has 
been developed in the organic division of the University of Illinois, 
which has been very successful in reducing many organic compounds. 

It was thot that it might also promote the reduction of nitric oxide. 



Preparation of the data! yiist - -About .4-. 5 gram of platinic 
chloride was dissolved in a mixture of 5 grams of sodium nitrate 










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I 1 $ 

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and 4 grams of potassium nitrate and the mixture evapotated to dry- 
ness on a water bath. It was then fused to a quiet liquid and 
allowed to cool, after which it was dissolved in water and filtered. 
The platinum precipitate on the filter paper was washed with water 
until free from salts. It was then washed into the pressure bottle 
and the filter paper saved to be used again to filter off the plat- 
inum after the run was completed. 

Procedure - -The solution in the pressure bottle was made 
acid with hydrochloric acid, the bottle evacuated and connections 
made. The bottle was shaken for six hours, the solution removed, 
filtered and evaporated to dryness. No residue was left showing 
that the platinum used as a catalyser did not have any effect in 
aiding hydrogen reduce nitric oxide. 

Mercury as the Catalvist - -Using the same pressure appar- 
atus as previously described, 15 grams of mercurous chloride and 
20 grams of stannous chloride were placed in the pressure bottle 
and 200 c.c. of water containing 15c. c. of dilute hydrochloric 
acid were added. The bottle was evacuated and connections made 
with the gas cylinder. The bottle was shaken for six hours and the 
gauge reading carefully observed. The mercurous chloride was re- 
duced to black metallic mercury by the stannous chloride. It was 
thot that the stannous chloride in conjunction with the hydrogen 
formed by the reaction would act as a reducing agent in the pre- 
«ence of metallic mercury as the catalyist. The gauge reading 
showed no decrease after the six hours. The solution was removed 
from the flask, almost neutralized by sodium hydroxide and the tin 



precipitated out by hydrogen sulphide. A small amount of the mer- 
cury was also precipitated by the hydrogen sulphide but the major 
amount was removed when the solution was filtered. The solution 
was then evaporated to dryness on a water bath and the residue tested 
for Hydroxylamine. The residue was composed completely of sodium 
chloride, no Hydroxylamine or ammonia being formed. 

Reduction by Chromous Chloride --Chesneau and Kohls chutter 
(loc.cit.)in their paper on the reduction of nitric oxide by means 
of chromous chloride found that when nitric oxide was passed into 
a neutral solution of chromous chloride that ammonia would be the 
final product while in an acid solution Hydroxylamine would be 
formed. They state, however, that nitric oxide must be passed into 
the acid solution of chromous chloride in order to secure Hydroxyl- 
amine, otherwise ammonia would be formed. A run was therefore made 
using chromous chloride in ian acid solution as a reducing agent. 

Preparation of the Chromous Chloride - -Metallic chronium 
was ground up to a fine powder and 100 c.c. of water and 50 c.c. of 
hydrochloric acid added. The mixture was then poured quickly into 
the pressure bottle which was then evacuated and connections made 
with the gas tank. 

Procedure - -The bottle was shaken for ten hours after which 
time the solution was removed, filtered and made alkaline with sodium 
hydroxide which precipitated all of the chronium. This was filtered 
off and the solution tested for Hydroxylamine. No reduction of the 
Fehling's solution took place. ihe solution was evaporated slightly, 



then made acidic, evaporated to dryness, and again tested for Hydro x- 
ylamine. After a negative result had been obtained it was tested 

for ammonia which was found to be present in considerable amounts. 

It is evident that the chroinous chloride caused the reduction to 
procede to ammonia and not to Hydroxylamine. It was thot, however, 
in view of Chesneau and Kohl s chut ter ' s work that some Hydroxylamine 
should have been formed. In order to ascertain if the above authors 
really secured Hydroxylamine as they claim, their work was repeated. 
The apparatus used is shown in Figure 4. Nitric oxide from a gas- 
ometer was passed rapidly into an acid solution of chromous chloride 
protected from air by a layer of petroleum ether. The residual gas 
was collected in another gasometer and again passed thru the chrora- 
ous chloride solution. This procedure was repeated several times, 
until a marked decrease in the volume of nitric oxide was observed. 
The solution was poured into a separatory funnel and the chroinous 
chloride solution drawn off. It was then made alkaline with sodium 
hydroxide and the precipitated chromium filtered off. The filtrate 
was evaporated to dryness and the residue tested for Hydroxylamine. 

No reduction of the Fehling's solution took place. It was then 
examined for ammonia \vhich was again found to be present in consider- 
able amounts. 

The experiment was again repeated, all possible care in 
following directions was taken, samples of the chromous chloride 
solution being tested every few minutes, but at no time could any 
positive test for Hydroxylamine be obtained. Altho Chesneau and 
Kohlschutter claim to have obtained Hydroxylamine in this manner. 






























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we do not believe it possible that Hydroxylamine could be formed 
and stay in the solution as Hydroxylamine in the presence of such 
a powerful reducing agent as chromous chloride. It may be possible 
that Hydroxylamine is formed as an intermediate product, but our 
belief is that it is immediately reduced to ammonia. 

Nickel as the Catalyser - -In view of previous research and 
our own results, it was decided that the platinum group could not be 
used as catalysers due to the fact that Hydroxylamine will decompose 
in the presence of colloidal platinum and platinum black. In a paper 
published by A. Findlay and W. Thomas the products of the decomposi- 
tion are said to be ammonia nitrogen and nitrous oxide. B.Adhikary 
(loc.cit.) did all his work at temperatures over 100 G. A search of 
the literature failed to reveal any statements regarding the use of 
lower temperatures. If at over 100° C nickel changes nitric oxide 
to ammonia, would it not be possible at temperatures up to 90 G that 
the reducing action would not be so strong and instead of reducing 
the nitric oxide to ammonia it might stop at Hydroxylamine? 

Preparation and Use of the Gatalyist --A nickel catalyser 
which had been prepared Dy reducing nickel nitrate, was put into the 
pressure bottle, water added, the bottle evacuated and connected to 
the gas cylinder. After opening up the cylinder valve, the bottle 
was shaken for three hours at ordinary temperature. No decrease 
could be observed in the gauge reading. The temperature of the 
solution was raised gradually by placing a small flame under the 
bottle and surrounding the shaking bottle by an asbestos box to 
keep the heat in. A temperature of about 80-90 C could be obtained 
in this manner. 



The bottle was shaken for three more hours, the flame remo- 
ved and the bottle with solution allowed to c^ol while shaking. 

The solution was filtered to remove the nickel, and a small amount 
of hydrochloric acid added to the filtrate. The latter was evapor- 
ated to dryness but no residue was left showing that at tempera- 
tures below 100 G nickel did not catalyse the reduction of nitric 
oxide in a water solution. 

Reduction by Means of ned Phosphorus - -Among the chemical 
properties of red phosphorus is listed the fact that concentrated 
nitric acid is reduced with almost explosive violence while dilute 
nitric acid evolves nitrous fumes in the presence of red phosphor- 
us. Because of the reducing action it appeared possible that the 
red phosphorus might also reduce nitric oxide. A mixture of the 
red phosphorus and water was put into the reactian bottle and nit- 
ric acid bubbled thru the solution. In conjunction with this 
method, red phosphorus and water were also put in the pressure bott- 
le, connection made with the gas cylinder and the bottle shaken for 
three hours. The nitric oxide in the gasometer was passed back and 
forth several times thru the reaction bottle. The solutions were 
taken from the reaction and pressure bottles, filtered and evapora- 
ted to dryness after 10 c.c. of hydrochloric acid had been added. 

) 

No residue is left proving red phosphorus would not cause the re- 
duction of nitric oxide. In another run potassium iodide was add- 
ed as a catalyser,but the result was similar to the first as no 
Hydroxylaraine was obtained. 



The Use o f Sodium Amalgam as the Re ducing Agent - -The reduc- 
tion of many organic compounds by sodium amalgam led to the belief 
that it might aid in the reduction of nitric oxide. An amalgam 
containing .214$ sodium was put into the pressure bottle, connec- 
tions made and the bottle shaken for eight hours. It was removed 
from the bottle, filtered to remove the amalgam, a small amount of' 
hydrochloric acid added and the solution evaporated to dryness. 

No residue was obtained. 

Catalytic Reduction by Means of Palladium Asbestos 

Sabatier and Senderens have shown that in the presence of palla- 
dium sponge previously saturated with hydrogen, nitric oxide is com- 
pletely converted into water and ammonia. Their work was repeated 
by us with the exception that instead of palladium sponge being 
used we worked with palladium asbestos. The two gases, nitric oxide 
and hydrogen were preheated before passing over the catalyist. 

A diagram of the apparatus is shown in Figure 5. Nitric oxide and 
hydrogen were passed thru gas-washing bottles containing sulphuric 
acid and then thru a short piece of heavy glass tubing about three- 
fourths of an inoh in diameter, where they were heated slightly. The 
preheated gases were then passed thru the catalyser tube containing 
the palladium into a dilute solution of hydrochloric acid. On exam- 
ination of the hydrochloric acid solution it was found to contain 
ammonium chloride only, no Hydroxylaraine being formed. 



Reduction b y Use of Sulphur Dioxide -- In Divers and Haga 
(loc.cit.) publication, state that they have obtained Hydroxy lamine 
using sodium nitrite and sodium sulphite according to the equation. 

NaN02 + 2Na2S03 + HOH +■ 4HC1 = NH20H HG1 3NaCl -f 2NaHS04 
It would seem from the above equation that sulphur dioxide is the 

Z3 

active reducing agent. Tanatar, however , claims that sulphur dioxide 
will attack Hydroxylamine reducing it to ammonium sulphate. Divers 
and Haga's method was repeated by us, all directions being carefully 
followed. Sodium nitrite and sodium sulphite were mixed in the pro- 
portions as given by the equation, water added and the hydrochloric 
acid added very slowly. The solution was evaporated to dryness, an 
absolute alcbhol extraction made but no Hydro xyiamine was found to 
be present. The method was again repeated but as before no test for 
Hydroxylamine could be obtained. It was noticed that on each addi- 
tion of the hydrochloric acid a sharp rise in temperature followed. 

To determine if this rise in temperature was the cause of the non- 
formation of Hydroxylamine, the flask was placed in an ice-salt bath 
about -10 J C. The hydrochloric acid was added very slowly to the 
solutions of the salts and at no time was the temperature above -5 G 
The solution was then placed in evaporating dishes and evap- 
orated to dryness. B efore evaporation the solution was boiled for 
an hour to expell as much as possible of the sulphur dioxide. On 
testing the residue, Hydroxylamine was found to be present, It was 
extracted with absolute alcohol and the alcohol distilled oil, leaving 
a small amount of Hydroxylamine sulphate as a residue. The separa- 
tion of Hydroxylamine sulphate from the by-products, sodium chloride 


















































































































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and sodium acid sulphate is not complete because of the tendency 

of these salts to occlude small amounts of Hydroxylamine sulphate. 
Several extractions are necessary to completely remove all the 
Hydroxylamine sulphate. It is important to note that unless the 
reaction is carried out at low temperatures and the hydrochloric 
acid added very slowly, no Hydroxylamine sulphate will be formed. 

A possible explanation for this fact is that at room temperatures, 
sulphur dioxide will attack the Hydroxylamine formed and convert it 
into ammonium sulphate, while at temperatures below G^C, sulphur 
dioxide will complete the reduction but will not act on the Hydrox- 
y 1 am in e formed. 

Since Hydroxylamine can be formed by the reduction of a 
nitrite, would it not be possible that nitric oxide could be reduced 
in a similar manner? Qn account of the very slight solubility of 
nitric oxide in water , advantage was taken of the fact that nitric 
oxide will form an addition compound with ferrous sulphate in 
Water solution. An apparatus such as shown in Figure 6, served the 
purpose very well. About 8-10 grams of ferrous sulphate was dis- 
solved in 600 c.c. of water and the solution ' poured into a large 
wide-mouthed bottle. Nitric oxide made from ferrous sulphate, 
potassium nitrate and dilute sulphuric acid was passed into the 
water solution until it became a dark brown color. Sulphur dio- 
xide made by dropping sulphuric acid on sodium bisulphate was also 
passed into the water solution. The bottle was then immersed in 
an ice-salt bath and the solution stirred vigorously with a glass 
stirrer. 


























































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1 






























ure 



Approximately 10 liters of nitric oxide and 15 liters of 
sulphur dioxide were passed into the solution. After shaking for 
an hour the solution turned to a white color. It was then removed, 
allowed to come to room temperature. A small amount of the sol- 
ution was tested with barium chloride, which gave a white precipi- 
tate showing that the sulphur dioxide had been oxidized to sulphu- 
ric acid» Sodium hydroxide was added to precipitate all the iron 
and the solution filtered. The filtrate was made acidic with 
sulphuric acid and evaporated to dryness. No test for Hydroxyl- 
amine was obtained. 

In all probability Hydroxy lamine was immediately reduced by 
the ferrous sulphate or by the sulphur dioxide. According to 
Tanar (loc.cit.) when a solution of Hydroxylamine sulphate is 
saturated with sulphur dioxide, kept over night and evaporated to 
dryness on a water bath, ammonium sulphate is formed. 

Reaction with Hydraztne --To ascertain whether hydrazine 

would reduce nitric oxide, about 10 grams of it in water solution 

flv vol*' 

was put into a bottle and nitric bubbled thru. Examination of 
the solution proved that no reduction had taken place. 



V. Discussion . 

It will be seen from our results that the preparation of 
Hydroxylamine by a strictly chemical method is difficult and, in 
many cases, without success, the direct cause of the failure to pro- 
duce Hydroxylamine by some of the methods tried was due mainly to 
the great susceptibility of Hydroxylamine to the action of many 
substances which either decompose it as quickly as it is formed or 
reduces it at once to ammonia. 

It should be noted that low temperatures are conducive to 
the production of . Hydroxylamine, higher temperatures causing the 
formation of ammonia, nitrogen and nitrous oxide. This fact pro- 
hibits the use of such catalyists as nickel, copper , iron, etc . , 
which require temperatures over 100 G before they become active 
and thus our work was confined to the use of the platinum group. 

It was shown that nickel in a x&ter* solution at 8 Q-9G G does not 
cause the reduction of nitric oxide. The action of the catalyist 
used in this research either caused the decomposition or reduction 
of the Hydroxylamine formed or else had no effect on the reaction. 
No catalyser has been found which would promote the reduction to 
Hydroxylamine and not to ammonia. 

Hydroxylamine sulphate was obtained us using Diver's and 
Haga's (loc.cit.) method, but the amount obtained was small and a 
complete extraction difficult. The attempt to reduce nitric oxide 
by sulphur dioxide in the presence of ferrous sulphate as might 
have been expected because of the action of both ferrous sulphate 
and sulphur dioxide in decomposing any Hydroxylamine formed. 



If it were possible to procure some substance, the addition of which, 
would cause the Hydroxylamine to be precipitated as soon as it were 
formed, the solution of this problem might be solved. 

VI. Summary . 

I. Nitric oxide will not be reduced in the presence of 
colloidal or finely divided platinum used as a catalyist. 

II. At temperatures below 100-C nickel is not active 
while at higher temperatures it will promote the reduction of 
nitric oxide to ammonia. 

III. Strong reducing agents such as chromous chloride 
reduce nitric oxide to ammonia, no Hydroxylamine being formed. 

IV. Salts of Hydroxylamine in a saturated solution of 
sulphur dioxide and in the presence of ferrous sulphate are reduced 
to ammonia, if allowed to stand at room temperature for several 
hours . 

V. Substances such as metallic mercury, red phosphorus, 
sodium amalgam, stannous chloride, and hydrazine do not cause the 
reduction of nitric oxide to proceed to the formation of Hydroxyl- 
amine . 






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VII. Bibliography . 




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B. 32,241-4 



(1399) .